AU2019201700A1 - Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants - Google Patents

Abstract

Abstract The invention relates to novel quaternized nitrogen compounds, to the production thereof, and to the use thereof as fuel additives and lubricant additives, such as in particular detergent additives, additive packages that contain said compounds, and fuels and lubricants to which said additive packages have been added. The invention further relates to the use of said quaternized nitrogen compounds as a fuel addition for reducing or preventing deposits in the injection systems of direct injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines having common-rail injection systems, and for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common-rail injection systems.

Description

Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants

This application is a divisional application of Australian Patent Application No. 5 2016273853, which in turn is a divisional application of Australian Application No.

2012277805. AU2012277805 claims priority from EP Application No. 11171763.3. The specification for each of these applications is entirely incorporated herein by reference.

The present invention relates to novel quaternized nitrogen compounds, to the preparation thereof and to the use thereof as a fuel and lubricant additive, more particularly as a detergent additive, to additive packages which comprise these compounds; and to fuels and lubricants thus additized. The present invention further relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of directinjection diesel engines, especially in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, and for minimizing power loss in directinjection diesel engines, especially in diesel engines with common-rail injection systems.

State of the art:

In direct-injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine. The advantage of the direct-injection diesel engines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds.

At present, essentially three methods are being used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump-nozzle system (unit-injector system or unit-pump system) and the common-rail system.

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1a

In the common-rail system, the diesel fuel is conveyed by a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The full pressure is always applied to the common rail, which enables multiple injection or a specific injection form. In the other injection systems, in contrast, only smaller variation in the injection is possible. The injection in the common

8429357_1 (GHMatters) P95787.AU.1

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2019201700 13 Mar 2019 rail is divided essentially into three groups; (1.) pre-injection, by which essentially softer combustion is achieved, such that harsh combustion noises Cnaliing^if) are reduced and the engine seems to run quietly; (2.) main injection, which is responsible especially for a good torque profile; and (3,} post-infoctton, which especially ensures a low NO* value.

in this poat4njection, the fuel is generally not combusted, but instead evaporated by residual heat in the cylinder. The exhaust gas/fuel mixture formed is transported to the exhaust gas system, where the fuel,, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NO*.

The variable, cylinder-individual Injection in the common-rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NO*), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, that engines equipped with common-rail injection systems can meet the Euro 4 standard theoretically even without additional particulate filters'.

in modern common-rail diesel engines, under particular conditions, for example when biodiesei-containfog fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds are used, deposits can. form on the injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, i.e, especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments in the injector construction, especially by the change in the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives, in the injection systems of modern diesel engines, deposits cause significant performance problems, it is common knowledge that such deposits in the spray channels can lead to a decrease in the fuel flow and hence to power loss. Deposits at the Injector tip., in contrast. Impair the optimal formation of fuel spray mist and, as a result, cause worsened combustion and associated higher emissions and increased fuel consumption, in contrast to these conventional “external* deposition phenomena, Internal deposits (referred to collectively as internal diesel injector deposits (IDIP)) in

W5132OPCT

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2019201700 13 Mar 2019 particular parts of the injectors, such as at the nozzle needle, at the control piston, at the valve piston, at the valve seat, In the control unit and in the guides of these components, also Increasingly cause performance problems. Conventional additives exhibit inadequate action against these IDtDs.

US 4,248,719 describes quaternized ammonium salts which are prepared by reacting an alkenyisuccln imide with a monocarboxyilc ester and find use as dispersants in lubricant oils for prevention of sludge formation. More particularly, for example, the reaction of poiyisobutylsuccinic anhydride (PIBSA) with N,N-dimethylaminopropylamine (DMAPA) end quatemization with methyl salicylate is described. However, use In fuels, more particularly diesel fuels, is not proposed therein. The use of PISS A with low bismaleation levels of < 20% is not described therein,

US 4,171,959 describes quaternized ammonium salts of hydrocartoyl-substituted succfnimides, which are suitable as detergent additives tor gasoline fuel compositions.

For quatemization, preference is given to using alkyl halides. Also mentioned are organic CrCrhydrocarbyl carbcxylates and sulfonates. Consequently, the quaternized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a Ca-Cr hydrocarbyl carboxylate or a C^Cr hydrocarbyl sulfonate group, The use of p IBS A with low bismaleation levels of < 20% is likewise not described therein,

EP-A-2 033 945 discloses cold flow Improvers which are prepared by quaternizing specific tertiary monoamines bearing at least one Ce-C^o-aikyl radical with a Ct-Ch-alkyI ester of specific carboxylic acids. Examples of such carboxylic esters are dimethyl oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate, Applications other than that of improving the CFPP value of middle distillates are not demonstrated In EP-A-2 033 945..

WO 2006/135881 describes quaternized ammonium sells prepared by condensation of a hydrocarbyi-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent quatemization by means of hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid, especially acetic add. Further quaternizing agents claimed in WO 2006/135881 are dialkyl

M/51320-PCT

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2019201700 13 Mar 2019 sulfates, benzyl halides and hydrocarbyl-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.

The quaternlzing agents used with preference in WO 2006/135881, however, have serious disadvantages such as: toxldty or carcinogenicity (for example in the case of dimethyl sulfate and alkylene oxides and benzyl halides}, no residue-free combustion (for example in the case of dimethyl sulfate and alkyl halides), and inadequate reactivity which leads to incomplete quatemization or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess of quaternlzing agent; for example in the case of dimethyl carbonate).

It. was therefore an object of the present invention to provide improved qua tern ized fuel additives, especially based on hydrocarbyl-substituted poiycarboxylsc acid compounds, which no longer have the disadvantages of the prior art mentioned,

Brief description of invention;

It has now been found that, surprisingly, the above object Is achieved by providing specific quaternized nitrogen compounds and fuel and lubricant compositions addltized therewith.

Surprisingly, the inventive additives thus prepared are superior in several ways to the prior art additives prepared in a conventional manner; they have low toxicity (caused by the specific selection of the quaternlzing agent, bum ashiessly, exhibit a high content of quaternized product, and allow an economic reaction regime in the preparation thereof, and surprisingly have improved handling properties, such as especially improved solubility, such as especially in diesel performance additive packages. At the same time, the inventive additives exhibit improved action with regard to prevention of deposits In diesel engines, as especially illustrated by the use examples appended.

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Detailed descfipfion of thejswention:

A1) Specific embodiments

The present invention relates especially to the following specific embodiments:

1. A fuel or lubricant composition, especially fuel composition, composing, rn a majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a fraction thereof which comprises a quatemized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by

a. reacting a high molecular weight hydrocarbyl-substituted poiycarboxyiic add compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the poiycarboxyiic acid, and comprising at least one quatemizable amino group, to obtain a quaternlzabl© hydrocarb^-’Substituted poiycarboxyiic acid compound (by addition or condensation), and

b. subsequent reaction thereof with a quatemizing agent which converts the at least one hereafter quatemizable, for example tertiary, amino group to a quaternary ammonium group, said quatemizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or poiycarboxyiic acid (especially of a mono- or dicarboxylic acid) or of an aliphatic poiycarboxyiic acid (especially dicarboxylic acid).

2. A fuel or lubricant composition, especially fuel composition, comprising, in a majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quatemized nitrogen compound (or a fraction thereof which comprises a quatemized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by reacting a quatemizable high molecular weight hydrocarbyi-substituted poiycarboxyiic acid compound comprising at least one quatemizable amino group with a quatemizing agent which converts the at least one hereafter quatemizable, for example tertiary, amino group to a quaternary ammonium group,

M/51320-PCT

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2019201700 13 Mar 2019 said quatemizing agent being the eikyl eater of a cydoaromatlc or cycloaliphatic monoor polycarboxylic acid (especially of a mono- or dicarboxyilc acid) or of an aliphatic polycarboxylic acid (especially dlearboxyiic acid).

3, The fuel composition according to either of the preceding claims, wherein about

1.1 to about 2,0 or about 1.25 to about 2,0 equivalents, for example 1.3, 1.4, 1.5, 1,.6, U, ΐ,δ or 1.9 equivalents, of quatemizing agent are used per equivalent of quatemizable tertiary nitrogen atom. By Increasing the proportion of quatemizing agent within the range claimed, distinct improvements in product yields can be achieved,

4. The fuel composition according to any of the preceding claims, wherein the hydrocarbyi-aubatituted polycarboxylic acid compound is a polyisobutenyisuoclnie acid or an anhydride thereof, said acid having a bismaieation level of equai to or less than about 20% or equal to or lass than about 15%, for example IS, 14,13,12,11,10, 9, 8,

7,6,5,4,3,2,1 or 0.1%.

Lower levels of blsmaleaOon can contribute to a distinct improvement in the solubility of the additive and/or compatibility of the constituents in the formulation of additive packages,

5, The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quatemizing agent is a compound of the general formula 1

RiQC(Q)R2 (1) in which

R? Is a low molecular weight hydrocarbyi radical, such as alkyl or alkenyl radical, especially a lower alkyl radical, such as especially methyl or ethyl,, and

Ra is an optionally substituted monocyclic hydrocarbyi radical, especially an aryl or cycioalkyl or cycloalkenyl radical, especially aryl such as phenyl, where the substituent is selected from OH, NHs, NOs, 0(0)0¾ and RiOC(O)-, in which Ri is as defined above and R₃ is H or R_?) where the substituent is especially OH. More particularly, the quatemizing agent is a phthalate or a salicylate, such as dimethyl phthalate or methyl sai icy late.

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6, The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the guatemizing agent is a compound of the general formula 2

R,OC(O)-A-C(O)ORu (2) in which

Ri and Ru are each Independently a low molecular weight hydrocarbyl radical, such as an alkyl or alkenyl radical, especially a lower alkyl radical and

A is hydrocarbylene (such as especially Ci«Cralkyiens or CjrGraikenylene).

7. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaiernized nitrogen ccwnpound has a number-average molecular weight in the range from 400 to 5000, especially 800 to 3000 cr 900 to 1500,

8., The fuel or lubricant composition, especially fuel composition,, according to any of the preceding embodiments, wherein the quatemizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates; particular mention should be made of alkyl salicylates, especially tower alkyl salicylates, such as methyl, ethyl and n· propyl salicylates.

9, The fuel or lubricant composition, especially fuel composition, according to embodiment 1, wherein the compound which is reactive (capable of addition or condensation) with the polycarboxylfc acid and comprises an oxygen or nitrogen group and at. ieast one quaternlzabie amino group is selected from a, hydroxyalkyl-substituted mono- or polyamines having at least one quaternlzable primary, secondary or tertiary amino group;

b, straight-chairs or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary' amino group and having at least one quatemizable primary, secondary or tertiary amino group;

c. piperazines, and particular mention should bo made of group a.

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10, The fuel or lubricant composition according to embodiment 9, wherein the compound which is reactive, especially capable of addition or condensation, with the polyoarboxylic acid and comprises an oxygen or nitrogen group and at least one qu stern iza bie ami no g rou p is selected from a, hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxys! kyI-substituted primary, secondary or tertiary diamines, b, straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; dh or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group; and particular mention should be made of group a,

11, The fuel composition according to any of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels and aikanol-containing gasoline fuels,

12, The fuel or lubricant composition., especially fuel composition, according to any of the preceding embodiments, wherein the hydrocarbyi-substituted polyoarboxylic acid compound Is a polyisobutenylsuccinic acid or an an hydride (P1BSA) thereof, said acid having a low bismaleation level, especially 10% or less than 10%, for example 2 to 9 or 3 to 7%, More particularly, such PiBSAs are derived from HR-ΡΙδ with an Mn in the range from about 400 to 3000.

More particularly, the above compositions are fuel compositions, in particular diesel fuels.

13, The reaction product obtainable by a process as defined in any of the preceding embodiments, especially according to embodiment 3, 4, 5, 8 and In particular embodiment 8,. 9 or 10, or quaternized nitrogen compound obtained from the reaction product by partial or foil purification.

M/5132OPCT

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2019201700 13 Mar 2019 to a particular configuration (A) of the invention, quatemized reaction products which are prepared proceeding from polyisobutenyisuqdnic acid or an anhydride thereof are provided, this compound having a bismaleation level of equal to or less than about 20% or equal to or less than about 15%, for example 15, 14, 13,12., 11, 10, 9, S, 7, 6, S, 4,

S 3, 2., 1, or 0,1%, This polyisobutenyisuccinic add compound is reacted (especially by addition or condensation} with a compound comprising at least one oxygen or nitrogen group reactive {addable or condensable) with the polyisobutenyisuccinic acid compound and containing at least one quatemizable amino group, and then quatemized.

In a particular configuration (B) of the invention, quatemized reaction products which are obtained by quaternization using an excess of quatemizing agent are provided. More particularly, about 1.1 to about 2,0 or about 1.25 to about 2,0 equivalents, for example 1,3, 1.4, 1..5, 1.6, 1.7, 1.8 or 1.9, equivalents of quaternizing agent are used per equivalent of quatemizable tertiary nitrogen atoms. Particularly useful quaternizing agents are those of the formula (1}, especially the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, m and i-propyl salicylate, and η-, I- or tertbutyl salicylate.

In a further particular configuration (C)_t configurations (A) and (B) are combined, I.e, the quatemizable compounds prepared from the above polyisobutenyisuccinic acid compounds according to configuration (A) are quatemized according to configuration (B).

14, A process for preparing a quatemized nitrogen compound according to embodiment 13, comprising the reaction of a quatemizable hydrocarbyksubstituted polyoarboxyic acid compound comprising at least one tertiary quatemizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycioaromafic or cycloaliphatic monoor polycarboxylic acid (especially of a mono* or dicarboxyiic add) or of an aliphatic poiycarboxylic acid (especially dicarboxyiic acid).

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IS.. The use of a reaction product or of a quaternized nitrogen compound according to embodiment 13 or of a compound prepared according to embodiment 14 as a fuel additive or lubricant additive, especially fuel additive, especially diesel fuel additive.

S

16. The use according to embodiment 15 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, as determined, tor example, In an XUDd test to CEC-F23*01, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail Injection systems, as determined, for example, in a DW10 test based on CEG-F-OS6-08,

17... The use according to embodiment 15 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DISS (direct injection spark ignition) and PF1 (port, fuel injector) engines,

IS. The use according to embodiment 15 as a dieselfuel additive, especially as a cold flow improver, as a wax antiseftllng additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the Intake systems, such as especially the

Internal .diesel injector deposits (IDIDs), and/or valve sticking In direct-injection diesel engines, especially in common-rail injection systems,

1S* An additive concentrate comprising, in combination with further diesei fuel or gasoline fuel additives, especially diesei fuel additives, at least one quatemized nitrogen compound as defined in embodiment 13 or prepared according to embodiment 14,

A2) General definitions

A condensation or condensation reaction in the context of the present invention describes the reaction of two molecules with elimination of a relatively small molecule, especially of a water molecule. When such an elimination is not detectable analytically; more particularly not detectable in stoichiometric amounts, and the two molecules react

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2019201700 13 Mar 2019 nevertheless, for example with addition, the reaction In question of the two molecules Is without condensation.

In the absence of statements to the contrary, the following general conditions apply:

’’Hydrocarbyl¹* can be interpreted widely and comprises both long-chain and shortchain, straight-chain and branched hydrocarbon radicals, which may optionally additionally comprise heteroatoms, for example Ο, N, NH_S S, in the chain thereof, ’’Long-chain” or high molecular weight” hydrocarbyl radicals have a number-average molecular weight (Μ_δ) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. More particularly, they are formed essentially from Cjm, especially Cjm, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof,, where the different monomers may be ccpoiymerited In random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as poiyaikyiene radicals or poty-C-M- or polyC2-4-alfcytene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO 2006/135581 and the literature cited therein,

Examples of particularly useful poiyaikyiene radicals are polyisobutenyl radicals derived from h'igh-reactivity polyisobutenes (HR-PiS) which are notable for a high content of terminal double bonds (of., for example, also Rath et al., Lubrication Science (1992), 11-2, 175-185). Terminal double bonds are alpha-olefinic double bonds of the type

Polymer—/ which are also referred to collectively as vinylidene double bonds. Suitable high30 reactivity poiyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 mol% cr greater than 85 mol%. Preference Is given especially to poiyisobutenes which have homogeneous polymer structures. Homogeneous polymer structures are possessed

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to an extent of at least 00% by weight and mere preferably to an extent of at least 95% by weight Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementloned range, in addition, the high-reactivity polyisobutenes may have a polydlspersUy In the range from 1.05 to 7, especially of about 1.1 to 2.5, for example of lees than 1.9 or less than 1,5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.

Particularly suitable high-reactivity polyisobutenes are, for example, the Glissopai brands from BASF SE, especially Gilssopai® 1000 (Mn«1000), Siissopal® V83 (Mn~55Q), Glissopai® 1300 (Mn = 1300) and Glissopai® 2300 (Mn*2300), end mixtures thereof. Other number-average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of particular molecular weight ranges,

PIBSA is prepared in a manner known In. principle by reacting PIB with, maleic anhydride (MAA), in principle forming a mixture of PIBSA and bismaieated PIBSA (BM

PIBSA, cf, scheme 1, below), which is generally not separated but used as such In further reactions. The ratio of the two components to one a nether can be reported via the bismalestion level (BML). The BML is known per se (see also US 5,883,198). The BML can also be determined by the following formula:

BML “ 100% x t(wt-%(BM PlBSA))/(wt-%(BM PIBSA)+wt~%{PIBSA))] where wt-% (X) represents the proportion by weight of component X (X. “ PIBSA or BM PIBSA) in the reaction product of PIB with MSA,

Scheme 1

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r'\

PIB MSA

PIBSA

O<s^O

T >0 9 '-A It s r' N i l ο .,Χ''-···Μ o

BSM P1BSA

Hydrocarbyl-substituted poly carboxylic acid compound with a low bismaleation Sever, especially corresponding polyfsobutenyisuccinic adds or anhydrides thereof (also referred to overall as PIBSA) are known from the prior art. Especially advantageous are bismaleation levels of 20% or lass, or 15% or less, for example 14, 13, 12 or 10%; or 10% or less, for example 2-0, 3-8, 4-7, 5 or 8%, The controlled preparation thereof Is described, for example, in US 5,883,198, Suitable for preparation thereof are especially the above Ngh-reactlvlty polyisobutenes with an Mn In the range from about 500 to 2500, tor example 550 to 3000, WOO to 2000 or 1000 to 1800,

A nonlimiting example of a corresponding PIBSA is Glissopai® SA, derived from HR-PIB (Mn = 1000), with a bismaleation level of 8%.

Short-chain hydrocarbyT or low molecular weight hydrocarbyT is especially straightchain or branched alkyl or alkenyl, opt tonally interrupted by one or more, for example 2, 3 or 4, heterootorn groups such as -O- or -NH-, or optionally mono- or poiysubsflttrted, for example di-, tri- or tetrasubstifuted.

Alkyl* or lower alkyl represents especially saturated, straight-chain or branched hydrocarbon radicals having 1 to 4,1 to 6, 1 to 8, or 1 to 10 or 1 to 20, carbon atoms, for example methyl, ethyl, n-propyi, 1-methylethyl, n-butyi, 1-methylpropyl, .2methyipropyl, 1,1-dimethylethyl, n-pentyl, 1»methyibutyl, 2-methylbutyl, 3-methylbutyl,

2,2-dlmethylprcpyi, i-efbylpropyl, η-hexyl» 1,1-dimethytpropyl, 1,2-dimethyipropyl, 1methyipentyi, 2-methylpentyl, 3-methyipentyl, 4-methyipentyl, 1,1-dlmethyibutyl, 1,.2dimethylbutyl, 1,3-dlmethyibutyl, 2,2-drmethylbutyl, 2,3-dimethylbuiyl, 3,3-dlmelhylbutyl, 1-ethy fouty I 2-ethyi butyl, 1,1,2-tr imef hy I propy 1, 1,2,2«tr imet by Ipropy I, 1 -ethyl-1 methyfpropyi and 1-eihyl-2-methyipropyi; and also n-heptyl, n-octyl, n-nonyl and n30 decyl, and the singly or multiply branched analogs thereof.

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2019201700 13 Mar 2019 “HydroxyafkyP reprosente especially the mono- or polyhydroxyiated, especially monohydroxylated, analogs of the above alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyeikyl groups with a primary hydroxyl group, such as hydroxymethyl,. 2-hydroxyethyl 3-hydroxypropyk 4-hydroxybutyk “Alkenyl* represents mono- or polyunsaturated, especially monounsaturated, straightchain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or .2 or to

20 carbon atoms and a double bond in any position, for example C2-Cralkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-mothytethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1meihyi-1-propenyl, 2-methyM-propenyl, 1-methyi-2-propenyl, 2-methyl-2-propenyl, 1pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyM-butenyl, 2-methyM-butenyi, 3methyl-1-butenyl, 1-methyl-2~butenyl, 2-mefhyk2-buten>4 3-methyl-2-butenyl, 1-methyl15 3-butenyl, 2-methyf-3-butenyl, 3-methyl -3-butenyl, 1₍1-dimethyl-2-propenyf, 1,2dimefhyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-etiyl-1-propenyl, 1-ethyl-2-propenyl, 1hexenyl, 2-bexenyl, 3-hexenyi, 4-hexenyl, 5-hexenyi, 1-methyM-pentenyl, 2-methyMpentenyl, 3»methyM-pentenyl, 4~ΓηβΐΚνΙ-1-ρδηί@ηνί_ϊ 1-methyl-2-pentenyl, 2-methyl-2pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyf~320 pentenyl, 3-methyl-3-pentenyl, 4-methyi~3-pentenyl, 1-methyM-pentenyl, 2-methyMpentenyl, 3-methyi-4-pentenyl, 4-methyl-4~pentenyl, 1,1-dimetoyl*2-butenyl, 1, 1-dlmethyl-3-butenyl, 1.,2-dimethyM-butenyf, 1,2-dimethyt*2-butenyi, 1 ,2-dimethyP3bufenyl, 1,3-dfmethyM-butenyl, 1,3-dimethyi-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2dlmethyl-3-butenyl, 2,3-dimethyM -butenyl, 2,3-dlmethyl-2-butenyl, 2,3-dimefhyl-325 butenyl, 3,3-dlmefoyM -butenyl, 3,3-dlmefoyl-2-butenyf, 1-ethyl-1 -butenyl, 1 -ethyl-2bntertyh 1-ethyl-3-bufenyl, 2-ethyl-l-butenyl, 2-ethyt-2-butenyl, 2-ethyl-3-butenyl, 1,1,2trimethyl-2-propenyl, l-efoyM-methyl-2-propenyl, 1-ethyl-2-methyl-l-propenyl and 1 -ethyl-2-methyi-2-propenyl.

“Alkylene* represents straight-chain or mono- or polybranched hydrocarbon bridge groups having 1 to 10 carbon atoms, for example CrCralkylene groups selected from -CH_r, -{CHsh-, -iCHOr, *CHjrCH{GHs}-> -CH(CH₃}-CH₂-, {CH_s)c, -(CH₂)rCH{CH3)-, -CH₂-CH(CH₃)-CHr, (CH₂>, -(«)«-> -CH(CH₃>CH_S-CH₂-CH(CH₃)or -CH(CHs}-CHrCHrCH2-CH{CHs)- or CrC4-alkylene groups selected from -CH2-, M/5132G-PCT

PF 0000071427 SE/Ab

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IS {CHg>, -(CHss)s- -CH_rCH(CH₃}-, -CH(CHa)-CHr, -(CH^CRChbh -CHs “Alkenylene” represents the mono- or polyunsaturated, especially monounsatureted, analogs of the above alkylene groups having 2 to 10 carbon atoms, especially C2-C7alkenylenes or CrC<-alkenylenes, such as -CH»CH-, -CH~CH-CH₂-_t -CHsrGH»CH-_t -CH=CH-CH_a-CHs-, -CHi-CH=CH-CH_r, -€H^CH₂“CH=CH-, -CH(CH₃j-CH^CH-, -CHrC(CH_s>CH~.

Cyclic hydrocarbyl radicals’* comprise especially:

cycloaikyl: cerbccyclic radicals having 3 to 20 carbon atoms, for example Cs-Ct2cycloaikyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyciohexyl, cycloheptyi, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cydododecyl; preference is given to cyclopentyl, cyciohexyl, cycloheptyl, and also to cyclopropylmethyl, cyclopropyiethyl, cyclobutylmethyl, cyclobuiylethyi, cyclopentylmethyl, cyclopeniylethyl, cyclohexylmethyl, or Ca-Cr-cydoalkyl such as cyclopropyl, cyctobutyl, cyclopentyl, cyclohexyl, cycloheptyi, cyclopropylmethyl, cyclopropyiethyl, cyclobutyl methyl, pyctopentytethyl, cyclohexylrneihyl, where the bond to the rest of the molecule may be via any suitable carbon atom.

- cycloalkenyl: monocyclic, monounsetorated hydrocarbon groups having 5 to 8, preferably up to Q, carbon ring members, such as cyciopenten-1-yl, cydopenten-3-yi, cyctohexen-l-yl, cyctohexen-3-yl and cyctohexen-4-yh aryl: mono- or polycyclic, preferably mono- or bicyolic, optionally substituted aromatic radicals having 6 to 20.,. for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as 1- or 2«naphthyi, tetrahydronaphthyl, fluorenyl, Indenyl and phenanthrenyl. These aryl radicals may optionally bear 1, 2., 3, 4, 5 or 6 Identical or different substituents.

“Substituents for radicals specified herein are especially, unless stated otherwise, selected from keto groups, -COOH, -CGG-alkyl, -OH, -SH_f -CN, amino, -NO& alkyl, or alkenyl groups..

The term about in the context of a stated figure or of a value range denotes deviations from the specifically disclosed values. These are usually customary deviations. These

M/51320-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019 may differ, for example, by ± 10% to ±0,1% from the specific values. Typically, such deviations are about ± 8% to ± 1% or ± S%, ± 4%,. ± 3% or ± 2%.

A3) Folycarboxylic add compounds and bydrocarbyl-substituted pclycarboxylfo acid compounds:

The polycarboxylic acid compounds used are aliphatic di- or polybaslc (for example trior fetrabasic), especially from di-,· tri- or teiracarboxylic acids and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely estertfied), and Is optionally substituted by one or more (for example 2 or 3), especially a long-chain alkyl radical and/or a high molecular weight hydrocarbyi radical, especially a poiyalkylene radical. Examples are Cs-Cis polycarboxylic acids, such as the dicarboxyllc acids malonic acid, succinic acid, gluteric acid, adipic acid, pimelic add, suberic acid, ezelalG add and sebacic acid, and the branched analogs thereof; and the tricarboxylic add citric acid;

and anhydrides or lower alkyl esters thereof of. The polycarboxylic acid compounds can also be obtained from the corresponding monounsaturated acids and addition of at least one long-chain aikyl radical and/or high molecular weight hydrocarbyi radical. Examples of suitable monounsaturated acids are fumaric acid, maleic add, itaconic acid.

The hydrophobic long-chain or high molecular weight hydrocarbyi radical which ensures sufficient solubility of the guaternized product in the fuel has a numberaverage molecular weight <M4 of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to £5 1500, Typical hydrophobic hydrocarbyi radicals include polypropenyl, polybutenyi and polyisobutenyl radicals, for example with a number-average molecular weight Μ» of 3500 to 5000, 350 to 3000, 500 fo 2500, 700 to 2500 and 800 to 1500.

Suitable hydrocarbyi-substituted compounds are described, for example, in

DE 43 19 572 and WO 2008/138836,

Suitable hydrocarbyl-substituted polycarboxylic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic add compounds. Dimeric forms comprise, for example, two add anhydride groups which

M/51320-PGT

PF 0000071427 SEfAb

2019201700 13 Mar 2019 can be reacted independently with the quaternizable nitrogen compound in the preparation process according to the invention.

A4) Quatemizing agents:

Useful quatemizing agents are In principle alt alkyl esters which are suitable as such and are those of a cyctoammatic or cycloaliphatic mono or polycarboxyilc acid {especially of a mono- or dicarboxyilc add) or of an aliphatic polycarboxyilc acid (especially dicarboxyilc add),

W

In a particular embodiment, however, the at least one quatemlzabie tertiary nitrogen atom Is guaternized with at least one quatemferng agent selected from

a) compounds of the general formula 1

RrQC(Q)R₂ (1) in which

Ri is a lower alkyl radical and

Rg is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH_S NW2, NO2, 0(0)01¼ and RuOC(OS In which Ru Is as defined above for Ri and R3 is H or Rp and

b) compounds of the general formula 2

R_?OC(O)-A-C(O)OR_?S (2) in which

R1 and Ru are each Independently a lower alkyl radical and A is hydroearbylene (such as alkylene or alkenylene).

Particularly suitable compounds of the formula 1 are those In which

M/S1320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

Ri is a Cr, C-r or Cb-alkyl radical and

R« is a substituted phenyl radical, where the substituent is HO* or an ester radical of the formula Ri«OC(O)- which is in the para, meta or especially ortho position to the RiGC(G)- radical on the aromatic ring,

Especially suitable quaternizing agents are the lower alkyl esters of salicylic add, such as methyl saficylate, ethyl salicylate, n- and hpropyl salicylate, and n*, i- or tert-butyl salicylate.

AS) Quaternized or quaternizable nitrogen compounds;

The quatemizabl© nitrogen compounds reactive with the polycarboxylie acid compound are selected from a, hydroxyaikyl-substituted mono or poiyamines having at least one quaternized (e.g. choline) or quaternizable primary; secondary or tertiary amino group;

b, straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic poiyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quaternizable primary, secondary or tertian·' amino group;

c, piperazines.,

The quaternizable nitrogen compound is especially selected from d, hydroxyaikyl-substituted primary, secondary, tertiary or quaternary 25 monoamines and hydroxyaikyl-substituted primary, secondary, tertiary or quaternary diamines;

e, straight-chain or branched aliphatic diamines having two primary amino groups; di* or polyamines having at least one primary and at least one secondary amino group; di* or poiyamines having at least one primary and at least one tertiary amino group; dl- or poiyamines having at least one primary and at least one quaternary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic poiyamines having two primary amino groups; aromatic or nonaromatic heterocydes having one primary and one tertiary amino· group.

M/S1320-PGT

PF 0000071427 SE/Ab

W

2019201700 13 Mar 2019

Examples of suitable hydroxyaikyi-substituted mono- or polyamines” are those provided with at least one hydroxyaikyl substituted, for example 1, 2, 3, 4, 5 or 6 hydroxyaikyl substituted,

Examples of hydroxyalkyi-substituted monoamines” Include: Nnhydroxyaikyl monoamines, Ν,Μ-άΙ hydroxyaikyl monoamines and Ν,Ν,Ν-irihydroxyalkyl monoamines, where the hydroxyaikyl groups are the same or different and are also as defined above, Hydroxyaikyl is especially 2-hydroxyethyl, 3~hy Proxy propyl or 4~hydroxybutyl, to

For example, the following hydroxyalkyi-substituted polyamines'’ and especially hydroxyalkyi-substituted diamines may be mentioned: (N-hydroxyalkyE)atkylenediamines, Ν,Ν-dihydroxyalkylaikyienediamines, where the hydroxyaikyl groups are the same or different and are also as defined above, Hydroxyaikyl Is especially 2« hydroxyethyl, 3-hydroxypropyl or 4-hydroxybufyh alkylene is especially ethylene, propylene or butylene.

Suitable diamines’* are alkylenediamines, and the N-alkyi-substifuted analogs thereof, such as N-monoalkylated alkylenediamines and the N,N- or Ν,Ν’-dialkylated alkylenediamines. Alkylene is especially straight-chain or branched Ci-r or Cm. alkylene as defined above. Alkyl is especially C-M-alkyl as defined above. Examples are especially ethylenediamine, 1,2-propylenediamine, 1,3-propylenedlamine, 1,4butyienedlamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and singly or multiply,, for example singly or doubly, Gs-Gt-alkylated, for example methylated, derivatives of the aforementioned diamine compounds such as 3-dimethyiamino-1propylamine (DMAPA), Ν,Ν-diefhylaminopropylamine and N,N-dimethyiaminoethylamine,

Suitable straight-chain polyamines’* are, for example, dial kylenetriam ine, trialkyleneteirsmine, tetraalkylenapentamina, peniaalkylenehexamlne, and the N-aikyl·substituted analogs thereof, such as N-monoaikylated and the N_:,N- or Ν,Ν’-dlaikylated alkylenepolyemlnes. Alkylene is especially straight-chain or branched Ci,?- or Cm. alkylene as defined above. Alkyl is especially CM-alkyi as defined above.

M/51.32C-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 is

Examples are tetraef hyienepentam ine tripropyienetetra mine, dibutyienetnamine, ramsne, d 'ipropylenetria mine, penta propy tenehexam Ine, tetrabutylenepenta mine, especial ly dfotby ienetriam ine, pentaethytenehexamine, tetrapropyfenepentamins, tnbutyfonetetram Ine, pentabutylenehexamine; and the Ν,Ν-diaiky! derivatives thereof, especially tie N.H-diCm-alRyl derivatives thereof. Examples include; Ν,Ν-dimethyidlmethylenetnarnine, Ν,Ν-diethyldimethylenetitamine, N,N-^propyIdimeth^enetriamine, N, Ndi methyldi ethylene-1,2-triamlne, N,N-diethyidiethylene-1,24riamine, N,Ndipropyldfethylene-1 .S-triamine, N,N-dimethyidipropylene-1,34rlamine (i.e. DMAPAFA),

N, N-dlet hyidi propylene-1,34 rlamln e, dimethyidibufyiene~l ,4-tdamine, dipropyidlbutyien e- i ,4»ti1amlne, diethyldipentytene-1,5-triamine, d im ethyidihexylene-1,6-tnamine, dipropyidihexylerse-1,6-tria m ine.

N,N-dlpropyidipropyiene-1»3-triamine, N,NΝ,Ν-dfefoyidlbutytene-t ,4-triamine, N, NH,N-dimethyldlpentylene-1,5-tdamine, N,NΝ,Ν-dipropyldipentylene-l ,5-trfamine, N,NΝ,Ν-diefoyidihexyfene-l ,8-triamlne and N,NAromatic carbocydlc diamines” having two primary amino groups are the diamino substituted derivatives of benzene, biphenyl, naphthalene, ietrahydronaphthaiene.

fluorene, Indene and phenanthrene.

Aromatic or nonaromatic heterocyclic poly amines” having two primary amino groups are the derivatives, substituted by two amino groups, of the following heterocycies;

-. 5» or 6-membered, saturated or monounsaturated heterocycies comprising one to two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms as ring members, for example tetrahydroforan, pyrrolidine, isoxazolidine, isothiazoldlne, pyrazolidlne, oxazolidine, thlazolldine, Imidazoildine, pyrroline, piperidine, pipeddinyi, 1,3-dioxane, tetrahydropyran, hexabydmpyrfdazine, hexahydropyrlmidine, piperazine·,

S-membered aromatic heterocycies comprising, in addition to carbon atoms, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, for example furan, Wane, pyrrole, pyrazoie., oxazole, thiazole, imidazole and 1,3,4-triazote; isoxazole, isothiazoie, thladiazoie, oxadiazoie;

W51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

6-membered heterocycles comprising, in addition to carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyridtnyi, pyrldazine, pyrimidine, pyrszinyi, 1,2/Mriaz.ine, 1,3,5-tria3dn-2-yl.

“Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group” are, for example, the abovemantioned N-heterocydes which are aminoaikylatad on at least one ring nitrogen atom, and especially bear an amino-Cw-alkyl group,

Aromatic or nonaromatic heterocycles having a tertiary amino group and a hydroxyalkyl group” are, for example, the abovementloned N-heterocycIes which are hydroxyalkylated on at least one ring nitrogen atom, and especially bear a hydroxy-C?. 4-sikyi group,

Mention should be made especially of the following groups of individual classes of quatemizabla nitrogen compounds:

M/51320-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019

Group I:

| Isomeric pentanediamlnes, for example

Isomeric bexanediamines, for exaropt

H,hk ⁵ '_V- _NhL

Isomeric heptanediamhes, for example

H₃N.

''NHn

DA andppfyem/ries wffb a secoridary second ritfrogew atom

Diet h ^enetnem ine (D ET A}

H,K

Dipropyteneiriamine (DPTA), 3,3'imiriobis( N ,N-d imethyi pro pyiamlne)

H/k

T rietriylerieUriram i ne (YET A)

T etraethylenepentamifie (ΤΕΡΑ) .^AWWWVWWVAH· I.

Pentaef bvle nehexam be

H

HJsL ..--''x, >N_S /\ _s *· jq ItSi.

H • NH_; 'N

H

NH

NFL

H?U

N'

H

H/f

HNs

H ,K 'i\r

H

M/513.20-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 | N-Metbyl-S-amino-l-propylamine i Btsbexamethyteneiriaroine

Aromaf&s | Diaminoberizanes, for example

Diaroinopyridines. for example

Group 2;

KME

-(3-A? i) i r?op_tropyi)iro idazoia

4-(3-Am:t'iopropyl)mo?'pbolrne

I 1 -(2-Amincethyl piperidine)

2-(1 -Plperaariyhetbyfamine (AEP)

I N^piperazine

I Arofogg wffft a tertiary second nffroger? .atom

3,3-Oiam Ine-N-m ethy Id ipropyiam ine

A-D tm eth yla m irto-1 -propyle m ine (D Μ APA)

N·

H

NH,

H

A, 'NH,

HJM>

h₂n ‘nm.

,,,Α. A

H₂N' n

FORMULA

M/l

O' 'N 'N / \ /--NH, f Vr / \ N— \_/

N U—

W / \

N hl·

KF’

KX 'Ν'

NH,

M/5132CLPCT

PF 0000071427 SE/Ab

x.

2019201700 13 Mar 2019

N, M-DseihyJajnjnopropyiarrs ins

JJ4, N Osmethylsm inoeth y la m ine

Group 3:

JAMS T

A/coriofe twffl a primary and secopcfaiy amfne

Ethanolamkre f 3-Hydroxy-H -propyism ine

Diethanolamine

I Diisepropanoiamrne

N-{2“Hydraxyethy)sthyIsned§amtne

Atopho/s wfrh a teri/ary awn/fte......

| Triethanolamine, {2,2\2%iitrilotrietlisoof} j 1 -(3-Hydroxyprop^)imidazote

H,bk ,³ N

FORMULA

H„hk '_0H κχ

HO

HO

HO' z\

OH

H

N“

ΌΗ

X.

OH

OH

J

k.

OH k-y

I

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 p

Tris(hydroxyrn$ihyl )amine

3-Dim e thy t a m ino 1 -propanol

3-Diethylam ino- i -props not | 2-Dimethyiamlno-l -ethanol T““ _ - —

A6) Preparation of inventive additives:

a) Reaction with oxygen or nitrogen group

The hydrocarbyl-substifutad polycarboxylic acid compound can be reacted with the quatemizable nitrogen compound according to the present invention under thermally controlled conditions, such that there is essentially no condensation reaction. More particularly, no formation of water of reaction is observed in that case, More particularly, such a reaction is effected at a temperature in the range from 10 to SOX, especially 20 to SOX or 30 to SOX, The reaction time may be in tile range from a few minutes or a few hours, for example about 1 minute up to about 10 hours. The reaction can be effected at a pressure of about 0,1 to 2 atm, but especially at approximately standard pressure. For example, an inert gas atmosphere, for example nitrogen, is appropriate,

More particularly, the reaction can also be effected at elevated temperatures which promote condensation, for example in the range from 90 to 100'C or 100 to 170^eC. M/5132G-PCT

PF 000007142? SBAb

2019201700 13 Mar 2019

The reaction time may be in the region of a few minutes or a few hours, for example about 1 minute up to about 10 hours. The reaction can be effected at pressure at about GJ to 2 atm, but especially at about standard pressure,

The reactants are initially charged especially in about equimolar amounts; optionally, a small molar excess of the polycarboxylic add compound, for example a 0.05- to 0.5fold, for example a O.i-to 0,3-fold, excess, is desirable, if required, the reactants can be initially charged in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, for example, solvents of the Soivess© series, toluene or xylene. The solvent can also serve, for example, to remove water of condensation azeotropicaliy from the reaction mixture. More particularly, however, the reactions are performed without solvent

The reaction product thus formed can theoretically be purified further, or the solvent

IS can be removed. Usually, however, this is not absolutely necessary, such that the reaction step can be transferred without further purification Info the next synthesis step, the quatemization,

b) Quatemization

The quatemization in reaction step (b) is then carried out In a manner known per se.

To perform the quatemization, the reaction product or reaction mixture from stage a) is admixed with at least one compound of the above formula 1 or 2, especially in the stoichiometric amounts required to achieve the desired quatemization. it is possible to use, for example, 0.1 to 2,0, 0.2 to 1,5 or 0,5 to 1.25 equivalents, of quatemizing agent per equivalent of quatemizable tertiary nitrogen atom. More particularly, however, approximately equimolar proportions of the compound are used to quatemize a tertiary amine group. Correspondingly higher use amounts are required to quaternize a secondary or primary amine group, in a further variant, the quatemizing agent is added in excess, for example 1,1 to 2.0, 1,25 to 2 or 1,25 to 1.75 equivalents of quatemizing agent per equivalent of quatemizable tertiary nitrogen atom.

Typical working temperatures here are In the range from 50 to 180*0, for example from

90 to 160*0 or 100 to 140“C, The reaction time may be in the range of e few minutes

M/S1320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 or a few hours, for example about 10 minutes up to about 24 hours. The reaction can be effected at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1,5 to 3 bar, but especially at about standard pressure.

if required, the reactants can be initially charged for the quatemization in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof, or a sufficient proportion of solvent from reaction step a) is stili present Typical examples are, for exam pie, solvents of the Soivesso series, toluene or xylene, The quatemization can, however, also be performed in the absence of a solvent, io

To perform the quatemization, the addition of catalytically active amounts of an acid may be appropriate, Preference is given to aliphatic monocarboxytic acids, for example Gt“C«-monocarboxylic acids such as especially lauric acid, isononanoic add or neodecanoic acid, The quatemization can also be performed in the presence of a

Lewis acid. The quatemization can, however, also be performed in the absence of any add,

c) Workup of the reaction mixture

The reaction end product thus formed can theoretically be purified further, or the solvent can be removed. In order to improve the further processability of the products, however, it is also possible to add solvent after the reaction, for example solvents from the Soivesso series, 2-ethylhexanot, or essentially aliphatic solvents. Usually, however, this is not absolutely necessary, and so the reaction product is usable without further purification as an additive, optionally after blending with further additive components (see below).

B) Further additive components

The fuel additized with the inventive quaternized additive Is a gasoline fuel or especially a middle distillate fuel, in particular a diesel fuel

The fuel may comprise further customary additives to improve efficacy and/or suppress wear.

W5132G-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019 in the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow Improvers, lubricity Improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number Improvers, combustion Improvers, antioxidants or stabilizers, antistats, metallocenes, metal deactlvetors, dyes and/or solvents.

In the case of gasoline fuels, these are in particular lubricity improvers (fnction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizer®, antistats, metallocenes, metal deactivatore, dyes and/or solvents.

Typical examples of suitable coeddiflves are listed in the following section:

81) Detergent additives 15

The customary detergent additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbon radical with a number-average molecular weight (Ma) of 85 to 20 000 and at least on© polar moiety selected from;

(Da) mono· or poiyamino groups having up to 8 nitrogen atoms, at ienst one nitrogen atom having basic properties;

(Db) nitro groups, optionally in combination with, hydroxyl groups;

(Dc) hydroxyl group® In combination with mono- or poiyamino groups, at least one nitrogen atom having basic properties;

(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;

(De) sulfonic acid groups or their alkali motel or alkaline earth metel salts;

(Of) polyoxy-G·?- to Cralkyiene moieties terminated by hydroxyl groups, mono- or poiyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups;

y/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 (Dg) carboxylic ester groups;

(Oh) moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or (Di) moieOes obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate soiubiiity In the fuel, has a number-average molecular weight (Mb) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 5000, even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500.. As typical hydrophobic hydrocarbon radicals, especially In conjunction with the polar especially poiypropenyi, polybutenyi and polyisofoutenyi radicals with a number-average molecular weight Μ» of preferably in each case 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to £500 and especially 800 to 1500 into consideration.

Examples of the above groups of detergent additives include the following;

Additives comprising mono- or polyamino groups (Da) are preferably polyalkenemonoor polyaikenepolyamines based on polypropene or on hlgh-reactivity (i.e. having predominantly terminal double bonds) or conventional (i.e, having predominantly Infernal double bonds) polybutene or polyisobutene having Μη = 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500, Such additives based on highreactivity polyisobutene, which can be prepared from the polyisobutene which may comprise up to 20% by weight of n-foutene unite by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethyiaminopropyiamin e, ethy fenedlam ine, d iethy ienetnami ne, tr iethylenetetramlne or tetraettiylenepentamin©, are known especially from EP-A 244 818. When polybutene or polyisobutene having predominantly internal double bonds (usually In the β and γ positions) are used as starting materials in the preparation of the additives, a possible

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used here for the amination may be, for example, ammonia, monoamines or the abovementioned potyamines, Corresponding additives based on polypropene are described in particular in WO-A 94/24231,

Further particular additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of polylsobutenes having an average degree of poiymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in psrticufar In WO-A 97/03946,

Further particular additives comprising monoamino groups (Da) are the compounds obtainable from poiyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described irs particular in DE-A 196 20 262.

Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polylsobutenes having an average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular In WO-A 96/03367 and in WO-A 96/03479, These reaction products are generafly mixtures of pure nitropolyisobutenes (e.g, ο,β-dinitropoiyisobutene) and mixed hydroxynitropolylsobutenes (e,g, a-nitro-βhydroxypolyisobutene),

Additives comprising hydroxyl groups in combination with mono- or polyamino groups (Dc) are in particular reaction products of poiyisobutene epoxides obtainable from poiyisobutene having preferably predominantly terminal double bonds and M_n ~ 300 to 5000, with ammonia or mono- or pofyamlnes, as described In particular in EP-A

476 485,

Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copofymers of Cr to C^oiefins with maleic anhydride which have a total molar mass of 500 to 20 000 and some or si I of whose carboxyl groups have been

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 converted to the alkali metal or alkaline earth mete! salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by EP-A 307 81S. Such additives serve mainly to prevent valve seat wear and can, as described in WO*A 87/01126, advantageously he used in combination with customary fuel detergents such as poly(iso)buteneamines or polyetheramanes.

Additives comprising sulfonic acid groups or their aikail metal cr alkaline earth metal salts (De) are preferably alkeli metal or alkaline earth metal salts of an alkyl suifosuccinate, as described In particular in EP-A 839 632. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poly(iso)buteneamines or poiyetheramlnes.

Additives comprising polyoxy-Cs-C^aikylene moieties (Df) are preferably poiyethers or

1S poiyetheramlnes which are obtainable by reaction of Cr to Ce<raikanols, Cr to C^alkanediols, mono or di-Cr to Cgg-alkyiamines, Cr to C^-alkyicyciohexanols cr Ci- to Csraikylphenols with 1 to 30 moi of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, In the case of the poiyetheramlnes, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and USA 4 877 416. In the case of poiyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butexyfetes,

Isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenoi butoxylates and propoxy tetes and also the corresponding reaction products with ammonia,

Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanois or polyols, in particular those having a minimum viscosity of 2 mm®/s at 100’C, as described in particular in DE-A 38 38 918. The mono-, di- or tricarboxylic adds used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, Isophthalates, terephthalates and trimellftetes of isooctanoi, of isononanoi, of isodecanol and of isotridecanol. Such products also have carrier ell properties,

M/51320-PCT

PR 0000071427 SB Ab

2019201700 13 Mar 2019

Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or especially imido groups (Oh) are preferably corresponding derivatives of alkyl· or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of poiyisobutenylsucdnic anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having M« ~ preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2300, even more especially preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a thermal route in an ene reaction or via the chlorinated polyisobutene. The moieties having hydroxyl and/or amino and/or amido and/or imide groups are, for example, carboxylic acid groups, acid amides of monoamines, add amides of dl· or polyamines which, in addition to the amide function, also have free amine group®, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with di-or palyamirtes which, in addition to the imide function, also have free amine groups, or diimides which are formed by the reaction of dl· or pofyamines with two succinic acid derivatives, In the presence of imido moieties D(h), the further detergent additive in the context of the present invention is, however, used only up to a maximum of 100% of the weight of compounds with betaine structure. Such fuel additives are common knowledge and are described, for example, in documents (1) and ¢2), They are preferably the reaction products of alkyl· or alkenyl-substituted succinic acids or derivatives thereof with amines and more preferably the reaction products of polylsobutenyl-substitirted succinic acids or derivatives thereof with amines. Of particular interest in this context are reaction products with aliphatic poiyamlnes (poiyalkyieneimines) such as especially .25 ethylened famine, dlethyienetriamlne, triethylenetetramine, fetraeihyienepentamine» pentaethyienehexamine and hexaethyleneheptamine, which have an imide structure.

Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substltuted phenols with formaldehyde and mono- or polyamines such as ethylenediamfne, diethylenetriamine, triethylenetetramine, fetraethyienepentsmine or dimethylaminopropyiamine, The poiylsobutenyi-substituted phenols may stem from conventional or hlgh-reactivify poiyisobufene having = 300 to 5000, Such ’’polyisobutene Mannich bases are described in particular in EP-A S31141.

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm by weight, in particular ISO to 1000 ppm by weight

B2) Carrier oifs

Carrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are the fractions obtained in crude oil processing, such as brightstock or base oifs having viscosities, for example, from the SH 500 to 2000 dass; but also aromatic hydrocarbons, paraffinic hydrocarbons and aikoxyaikanols. Likewise useful is a fraction which is obtained in the refining of mineral off and is known as hydrocrack oil (vacuum distillate cut having a boiling range from about 360 to 500*0, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized under high pressure and also deparaffinlzed). Likewise suitable are mixtures of the abovementioned mineral carrier oils,.

Examples of suitable synthetic carrier oils are polyolefins (poiyaiphaoiefins or polyinternalolefins), (polyjesters, (poly)alKoxylatss, polyethers, aliphatic poiyether20 amines, aikyfphenol-started polyethers, aikyiphenoi-started polyetheramines and carboxylic esters of long-chain alkanols.

Examples of suitable polyolefins are olefin polymers having M_s« 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated),

Examples of suitable polyethers or polyetheramines are preferably compounds comprising polyoxy-Cs- to Cralkylene moieties which are obtainable by reacting Cr to Caralkanols, C«- to Cas-alkanediols, mono- or di-Ca» to Cge-aikylamines, C?- to Car alkyicycfohexanols or Cr to Gas-alkylphenols with 1 to 30 moi of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines, Such products are described in particular in EF-A 310 875, EP-A 356 725, EP-A 700 085 and U5-A 4,877,416- For example, the polyetheramines used may be poly-Gr to C$~sikytene oxide amines or functional

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 derivatives thereof, Typical examples thereof are trldeeanol butoxylates or isotridecanol butoxylates, fsononyfphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.

Examples of carboxylic esters of long-chain aikanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain aikanols or polyols, as described in particular in DE-A 38 38 918. The mono-, di« or tricarboxylic acids used may be aliphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, for example, 8 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthafates and trfmeliitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalate.

Further suitable carrier oil systems are described, for example, in DE-A 38 26 608,

DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 817.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably -about 5 to 30, more preferably 10 to 30 and especially 15 to 30 Ca- to C$-aIkylene oxide units, for example selected from propylene oxide, n20 butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain aikanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched C«- to Cte-alkyi radical. Particular examples include trfdecsnoi and nonyiphenol Particularly preferred alcohol-started polyethers are the reaction products (polyetherftication products) of monohydhc aliphatic Cr to Cmalcohols with Cr to GraSkytene oxides. Examples of monohydrlc aitphattc CtrCir alcohols are hexanol, heptanol, octanof, 2-ethylhexanol, nonyl alcohol, decanol, 3propylheptanol, undecanol, dodecanol, iridecanoi, tetradecanol, pentadecanol, hexadecanol, oetadecanoi and the constitutional and positional isomers thereof. The alcohols can be used either In the form of the pure isomers or in the form of technical grade mixtures. A particularly preferred alcohol rs tridecsnoL Examples of Cs- to Cr alkyiene oxides are propylene oxide, such as 1,2-propyiene oxide, butylene oxide, such as 1,2~butyiene oxide, 2,3-butylene oxide, isobutylene oxide or telrahydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to CsM/5132G-PGT

PF 0000Q71427 SE/Ah

2019201700 13 Mar 2019

3$ to Crslkytene oxides, i.e, propylene oxide such as 1,2-propylsne oxide and butylene oxide such as 1 ,2-butyJene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.

Further suitable synthetic carrier oils are afkojQflated alkyIphenols, as described in

DE-A 10 102 913.

Particular carder oils are synthetic carrier oils, particular preference being given to the above-described alcohol-started poiyethers,

The carrier oil or the mixture of different carder oils is added to the fuel in an amount of preferably 1 to WOO ppm by weight, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight.

B3) Cold flow improvers

Suitable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate feels or diesel feels under cold conditions. For the intended purpose, they must have sufficient oil solubility, In particular, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improvers, MDFls) typically used in the case of middle distillates of fossil origin, I.e, in the case of customary mineral diesel fuels. However, It Is also possible to use organic compounds which partly or predominantly have the properties of a wax antisettling additive (WAS A) when used in customary diesel fuels. They can also act partly or predominantly as nucleators. it Is, though, also possible to use mixtures of organic compounds effective as MDFis and/or effective as WASAs and/or effective as nucleators.

The cold flow improver is typically selected from (K1) copolymers of a Cs- to C«®-olefin with at least one further ethylenicalfy unsaturated monomer;

(K2) comb polymers;

(K3) polyoxyaikylenes:

(K4) polar nitrogen compounds;

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 (KS) sulfocarboxyllc acids or sulfonic acids or derivatives thereof; and (K6) poly{meth)acrylic esters...

it is possible to use either mixtures of different representatives from one of the particular classes (K1) to (K8) or mixtures of representatives from different classes (K1} to (K6),

Suitable Cr to C4e-oiefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond.

In the latter case, the carbon-carbon double bond may be arranged either terminally ίαolefins) or internally. However, preference is given to α-olefins, more preferably aolefins having 2: to 8 carbon atoms, for example propene, 1-butene, 1-pentene, 1hexene and in particular ethylene.

in the copolymers of class (K1}, the at least one further ethylenicaily unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylio esters and further olefins,

When further olefins are also oopolymerized, they are preferably higher In molecular weight than the sbovementiened Cr to C^e-olefln base monomer. When, for example, the olefin base monomer used is ethylene or propene, suitable further olefins sre in particular Cia- to C-w-a-oiefins, Further olefins are in most cases only additionally oopolymerized when monomers with carboxylic ester functions are also used,

Suitable (meth)acrylic esters are, for example, esters of imethjacrylic acid with Cr to Cjgj-alkanofs, especially Cr to C^-alkanofs, In particular with methanol, ethanol, propanol, rsopropanoi, n-bufanoi, sec-butanoi, Isobutanol, tert-butanol, pentanol, hexanol, heptane!, octanol, 2-ethylhexanoi, nonanoi and decanol, and structural isomers thereof.

Suitable alkenyl carboxylates are, for example, Grto G«-alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 cartoon atoms, whose hydrocarbon radical may be linear or branched- Among these, preference is given to

M/51320-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019 the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference Is given to those whose branch is in the a-position to the carboxyl group, the e-carbon atom more preferably being tertiary, i.e. the carboxylic add being a socalled neocarboxylic add. However, the hydrocarbon radical of the carboxylic acid is preferably linear.

Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyf esters, preference being given to the vinyl esters. A particularly preferred alkenyl carboxylate Is vinyl acetate; typical copolymers of group (Kt) resulting therefrom are ethylene-vinyl acetate copolymers fEVAs), which are some of the most frequently used. Ethylene-vinyl acetate copolymers usable particularly advantageously and their preparation are described in WO 99/29748.

Suitable copolymers of class (K1) are also those which comprise two or mors different alkenyl carboxylates in oopolymehzed form, which differ in the alkenyl function and/or in the carboxylic acid group. Likewise suitable are copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (methjacrylic ester In copolymerized form,

Terpolymers of a Cr to C^-rx-olefln, a Cr- to G^-aSkyi ester of an ethyienlcalSy unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a Cr to Cw-alkenyl ester of a saturated monocarbo^ic add having 2 to· 21 carbon atoms are also suitable

2S as copolymers of class (K1), Terpolymers of this kind are described in WO

2005/054314. A typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or the further ethyienicaiSy unsaturated monomers) are copolymerized in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer. The main proportion in terms of weight of the monomer units in the copolymers of class (K1) therefore originates generally from the C₂ to C« base olefins.

M/51320-PCT rr iwaw/HZ/ iSfc/Αδ

2019201700 13 Mar 2019

The copolymers of class (K1) preferably have a number-average molecular weight M_R of 1000 to 20 000, more preferably 1000 to 10 000 and In particular 1000 to 8000.

Typical comb polymers of component (K2) are, for example, obtainable by the copolymerteatton of maleic anhydride or fumaric acid with another ethyfenicaily unsaturated monomer, for example with an «χ-olefin or an unsaturated ester, such as vinyl acetate, and subsequent, esterification of the anhydride or add function with an alcohol haying at least 10 carbon atoms. Further suitable comb polymers are copolymers of α-olefins end esterified comonomers, fee* example esterified copolymers of styrene and mateic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfomarates or poiymaleaies. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in Comb-Like Polymers. Structure and Properties, M A,. Plate and

V. P, Shtbaev, J. Poly, Sci. Macromolecular Revs. 8, pages 117 to 253 {1074). Mixtures of comb polymers are also suitable,

Polycxyalky tones suitable as components of class (K.3) are, for example, polyoxyalkylene esters,, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably af least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000, Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4,491.455, Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of TOO to 5000. Additionally suitable are polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.

Polar nitrogen compounds suitable as components of class (K4) may be either ionic or nonlonlc and preferably have at least one substituent, in particular at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NR^? in which R⁷ Is a Gr to C^-hjdrocsrbon radical. The nitrogen substituents may also be quatemized, i.e. be in cationic form. An example of such nitrogen compounds is that of ammonium salts and/or amides which are obtainable by the reaction of at least one

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019 amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably comprise at least one linear Cr tc C+o-alkyl radical Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for exam pie, octylamine, nonyiamine, decylamine, undecylamine, dodecyiamine, tetradecylamlne and the higher linear homologs. Secondary amines suitable for this purpose are, for example, dtoctadecylamlne and methylbehenylamine. Also suitable for this purpose are amine mixtures, In particular amine mixtures obtainable on the industriaS scale, such as fatty amines or hydrogenated tallamlnes, as described, for example, in Ulimann's

Encyclopedia of Industrial Chemistry, 6th Edition, Amines, aliphatic chapter. Adds suitable for the reaction are, for example, cyclohexane-1 ,2-dicarboxylic acid, cyclo hexene-1,2-dicarboxyllc acid, cyciopentane-1,2-dicarboxyiic add, naphthalenedtcarboxylic acid, phthalic acid, isophthalic acid, terephthaflc add, and succinic acids substituted by long-chain hydrocarbon radicals, in particular, the component of class (K4) is an oil-soluble reaction product of poly (Cato· Cgg-carboxylic acids) having at feast one tertiary amino group with primary or secondary amines. The poiyfCr to Cso-carboxylic acids) which have at least one tertiary amino group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic add units In the polycarboxyilc adds have preferably 2 to 10 carbon atoms, and are espedaily acetic add units. The carboxylic acid units are suitably bonded to· the polycarboxyilc adds, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are bonded via hydrocarbon chafes.

The component of class (K4) is preferably an oil-soluble reaction product based on poly(Cr to C^-carboxylic adds) which have at least one tertiary' amino group and are of the general formula Ha or lib

HOCXT .CGQH S B

HOOC.„xN. _Λ A_„CQ0H

Ο ·γί· O / i j a V

M/51320-FCT rr yww/W/ bfc/Ab

2019201700 13 Mar 2019 hooc^bn^bcooh

I

A

COOH (Hb) in which the variable A is a straight-chain or branched C2» to Cg-alkylene group or the moiety of the formula Hl

HOGCf⁸’ _HXH_e-CH_£CMjrCMjr (HI) and the variable 8 is a Cs- to Cir-alkylene group. The compounds of the general formulae Ila and Hb especially have the properties of a WASA,.

Moreover, the preferred oil-soluble reaction product of component (K4), ©specially that of the general formula Ha or HP, is an amid©, an amide-ammonium salt or an ammonium self In which no, one or more carboxylic add groups have been converted to amide groups,

Straight-chain or branched C2- to Ce-alkylane groups of the variable A ar©, for example, 1,1-ethylene, 1,2-propyiene, 1,3-propylerte, 1,2-butyiene, 1,3-butylene, 1,4-birtylen©, 2’roethyM,3-propylene, 1,5-pentylene, 2-methyM ,4-butylene, 2,2«dimethyM,3propylene, 1,6-hexylene (hexamethyiene) and in particular 1,2-ethylene, The variable A £0 comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.

Cr to Cis-alkylene groups of the variable B are, for example, 1,2*ethyiene,

1,3-propyiene, 1,4-butylene, hexamethyiene, octamethylene, decamethylene, dodeoamethyiene, tetradecamethylene, bexadecamethylene, octadecamethylene, nonadecamethyfene and especially methylene. The variable 8 comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.

The primary and secondary amines as a reaction partner for the polycarboxylto acids to form component (K4) are typically monoamines, especially aliphatic monoamines.

These primary and secondary amines may be selected from a multitude of amines which bear hydrocarbon radicals which may optionally be bonded to one another.

M/51320-PGT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

These parent amines of the oil-sotuble reaction products of component (K4) are usually secondary amines and have the general formula HN(R®}j> in which the two variables R® are each Independently straight-chain or branched to Catralkyl radicals, especially

Ci*- to C^-aikyl radicals. These relatively Song-chain alkyl radicals are preferably straight-chain or only slightly branched, in general, the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals, derive from naturally occurring fatty acid and from derivatives thereof. The two R® radicals are preferably Identical.

The secondary amines mentioned may be bonded to the poSycarboxylic acids by means of amide structures or in the form of the ammonium salts; it Is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups are present The oil-soluble reaction products of component (K4) are preferably present completely in the form of the amide structures,

Typical examples of such components (K4) are reaction products of nitriiofhacefc acid, of ethylenediamineteiraacetic acid or of propylene-1,2-dlamlnetetraacetic acid with in each case 0,5 to 1,5 mol per carboxyl group, especially 0.8 to 1,2 mol per carboxyl group, of dioieylamine, dips.imifina.mine, dicoconut, fatty amine, distearylamine, dibehsnyismine or especially ditallow fatty amine, A particularly preferred component (K4) is the reaction product of 1 mol of ethyienedlaminetetraacetic acid and 4 moi of hydrogenated dlteliow fatty amine.

Further typical examples of component (K4) include the Ν,Ν-dfalkylammonlum salts of 2-N\N’-diatkylamidobenzcates, for example the reaction product of 1 moi of phthalic anhydride and 2 moi of ditallow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 moi of an alkenylspirobisiactone with 2. mol of a dialkyiamine, for example ditaliow fatty amine and/or tallow fatty amine, the lest two being hydrogenated or unhydrogenated,

Further typical structure types for the component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic add-containing polymers, as described in WO 93/18115.

M/5132O-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

Sulfocarboxyiic adds, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of class (K5) are, for example, the oii-solubie carboxamides and carboxylic esters of oriho-suifobenzoic add, in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described In eP-A 261 957,

Poly (melb)acry lie esters suitable as co id flow improvers of class (K6) are either homo or copolymers of acrylic and methacrylic esters, Preference is given to copolymers of at

W least two different (methjacrylic esters which differ with regard to the esterifiad alcohol The copolymer optionally comprises another different oieflnically unsaturated monomer in copoiymerlzed form, The weight-average molecular weight of the polymer is preferably 50 000 to 500 000, A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated Cm and alcohols, the acid' groups having been neutralized with hydrogenated taliamine. Suitable poiy(meth)acrylic esters are described, for example, in WO 00/44857,,

The cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel In a fetal amount of preferably 10 to 5000 ppm by weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm by weight and especially of 100 to 700 ppm by weight, ter example of 200 to 500 ppm by weight,

B4} Lubricity Improve rs

Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty add esters, Typical examples are fell oil fatty acid, as described, for example, in WO 98/004656, and glyceryl monooleate. The reaction products, described In US 6 743 266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamlnes are also suitable as such lubricity improvers.

M/51320-PCT

PF 0000071427 SE/Ab

2019201700 13 Mar 2019

BS) Corrosion inhibitors

Suitable corrosion Inhibitors are, for example, succlrtic esters, in particular with polyols, fatty acid derivatives, for example oiefo esters, oligomerized fatty acids, substituted ethanolamlnes, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HITEC S36 (Ethyl Corporation).

B8) Demulsifiers

Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol· and naphthalenesulfcnates and the alkali metal or alkaline earth metal salts of fatty adds, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxyiates, phenol alkoxylates, e,g, tert-butylphenol ethoxylate or tert-pentyiphenol ethoxylate, fatty acids, alkjdphenois, condensation products of ethylene oxide (EG) and propylene oxide (PO), for example including In the form of EO/PO block copolymers, polyethylene! mines or else pofysiloxanes.

67} Dehazers

Suitable deha2ers are, for example, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2883 (Petrolite),

68} Antifoams

Suitable antifoams are, for example, polyether-modltied poiyslfoxanes, for example the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).

89) Cetane number improvers

Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyi nitrate and peroxides such as di-tert-butyl peroxide.

M/51320-PCT

PF 0000071427 SE/Ab .44

2019201700 13 Mar 2019

BIO) Antioxidants

Suitable antioxidants are, for example substituted phenols, such as 2,8*di-tert“ butylphenoi and ^-dl-terbbutyhS-methyiphsnoi, and also phenylenedfamines such as

N,N’-dl-seo-butyi-p-phenyienediamlne.

Bi 1) fotetei deactivators

Suitable metal deactivated are, for example, salicylic acid derivatives such as 10 N,N’-disaticylldene’1,2-propanedlamine,

812) Solvents

Suitable solvents are, for example, nonpolar organic solvents such as aromatic and 15 aliphatic hydrocarbons, for example toluene, xyienes, white spirit and products sold under the trade names SHELLSGL (Royal Dutch/Shell Group) and EXXSGL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanoi, decanot and isotrldecanol. Such solvents are usually added to the diesel feel together with the aforementioned additives and coaddiiives, which they are

Intended to dissolve or dilute for better handling.

C) Fuels

The Inventive additive is outstandingly suitable as a fuel additive and can be used in 25 principle in any fuels. It brings about a whole series of advantageous effects in the operation of internal combustion engines with fuels. Preference is given to using the inventive quatemixed additive in middle distillate fuels, especially diesel fuels.

The present invention therefore atsn provides fuels, especially middle distillate fuels,. 30 with a content of the inventive quatemfeed additive which Is effective as an additive for achieving advantageous effects in the operation of internet combustion engines, for example of diesel engines, especially of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems. This effective content (dosage) is generally 10 to 5000 ppm by wight, preferably 20 to 1500 ppm by weight especially

M/51320-PCT

FF 0000071427 SE/Ab

2019201700 13 Mar 2019 to 1000 ppm by weight, In particular 30 to 750 ppm by weight, tossed to each case on the total amount of fuel.

Middle distillate fuels such as diesel fuels or heating oils are preferably mineral oil raffinates which typically have a boiling range from 100 to 400*C. These are usually distillates having a 95% point up to 380*C or even higher. These may also be so-cailed ultra low sulfur diesel” or city diesel, characterized by a 95% point of, for example, not more than 345’C and a sulfur content of not more than 0,005% by weight or by a 95% point of, tor example, 285*0 and a sulfur content of not more than 0.001% by weight in addition to the mineral middle distillate fuels or diesef fuels obtainable by refining, those obtainable by coal gasification or gas liquefaction (gas to liquid (GTL) fuels) or by biomass liquefaction f biomass to liquid (8TL) fuels] are also suitable. Also suitable are mixtures of the aforementioned middle distillate fuels or diesel fuels with renewable fuels, such as biodiesel or bloetbanof, 15

The qualities of the heating oils and diesel fuels are laid down In detail, for example, in DIN 51603 and ΕΝ 590 (cf. also Ufimann’s Encyclopedia of industrial Chemistry, 5th edition, Volume A12, p, 617 to).

in addition to the use thereof in the abovemeniioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quaternized additive can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term middle distillate fuel in the context of the present invention. They are commercially available and usually comprise the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, especially of 3 io 10% by weight, baaed on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil..

Biofuel olis are generally based on fatty acid esters, preferably essentially on alkyl 30 esters of fatty acids which derive from vegetable and/or animal oils and/or fats. Alkyl esters are typically understood to mean lower alkyl esters, especially CrCL-alkyl esters, which are obtainable by transesferifying the glycerides which occur in vegetable and/or animal oils and/or fats, especialiy triglycerides, by means of lower alcohols, for example ethanol or in particular methanol f FAME?). Typical lower alkyl esters based

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2019201700 13 Mar 2019 on vegetable and/or animal oils and/or fats, which tinct use as a biofuel oil or components thereof, are, for example, sunflower methyl ester, palm oil methyl ester (TME), soya bit methyl ester (W) and especially rapeseed oil methyl ester CRIME”).

The middle distillate fuels or diesel fuels are more preferably those having a low sulfur content, i.e, having a sulfur content of less than 0,05% by weight, preferably of less than 0.02% by weight, more particularly of lass than 0.005% by weight and especially of less than 0.001% by weight of sulfur,

Useful gasoline fuels include all commercial gasoline fuel compositions, One typical representative which shall be mentioned here Is the Eurosuper base fuel to EM 228, which is customary on the market. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.

The inventive quatemized additive is especially suitable as a fuel add ill ve In fuel compositions, especially in diesel fuels, for overcoming the problems outlined at the outset in direct-injection diesel engines, in particular in those with common-rail injection systems.

The invention is now illustrated in detali by the working examples which follow. The test methods described herein are not restricted to the specific working examples, but are part of the general disclosure of the description and can be employed generally In the context of the present invention.

A. General test methods 30

Engine test b1) XUD9 test ™ determination of flow restriction

The procedure was according to the standard stipulations of GEG F-23-01,

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52) DWW - keep clean test

To examine the influence of the inventive compounds on the performance of directinjection diesei engines, the power toss was determined on the basis of the official test method CEC F-0S8-08. The power loss is a direct measure of formation of deposits in the injectors.

The keep clean test is based on CEC test procedure F-O93-QS Issue 5, The same fast setup and engine type (PEUGEOT DW10) as In the CEC procedure are used,

Special features of the test used;

a) Injectors

In the tests, cleaned injectors were used. The cleaning time in an ultrasound bath in 15 water at 60* C + 10% Superdecontamine {intersclences, Brussels) was 4 h,

b) Test run times toe test period was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-098-G8 was run through 12 times.

| toad | Torque | Charge dr j (%) J (Nm) j temperature

Stage | Duration j Engine speed j | (minutes) (rpm)

+/- 5 downstream of J charge run cooler j CG?+A3

M25G [3000

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* for range to be expected see CEC-Q98-Q8 ** target value

c) Power determination

The initial power (Pa, KC (Wj) is calculated from the measured torque at foil load 4000/min directly after the test has started and the engine has warmed up. The procedure is described in Issue 5 of the test procedure CEC F-S8-08, The same test setup and the PEUGEOT DWW engine type are used,

The final power (Ρ^, KC) Is determined in the 12th cycle In stage 12, (see table above). Here too, toe operating point is foil load 4000/mto. P_e^_f KC (kWJ Is calculated from the measured torque.

The power loss In KC is calculated as follows:

power loss. KC [%] ® (1 - P_8f«j,KC / Pe,KC) x 100

The fuel used 'was a commercial diesel fuel from Haltermann (RF-06-03). To 20 synthetically induce the formation of deposits at toe injectors, 1 ppm of zinc wss added thereto in the form of s zinc neodecenoate solution.

B. Preparation examples:

Reactants used:

PIBSA: Prepared from maleic anhydride and FIB 1000 In a known manner. For the Inventive preparation examples and comparative examples which follow, qualities with hydrolysis numbers in the region of 84*95 mg KOH/g were used. OMAPA was used with the particular PIBSA quality in a molar ratio of 1:1 according to the hydrolysis number. The PIBSA qualities used had blsmaleation levels (BML) of less than 15%,

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DMAPA; M = 102.18 methyl salicylate.: M 152,.14 dimethyl phthalate: M ~ 194,19 dimethyl oxalate; M ~ 118.00 dimethyl sulfate: M ~ 126,13 dimethyl carbonate M ~ 90.08

Preparation example 1; Synthesis of an inventive quaternized succinimide 10 (PIBSAfDMAPA/dimethyl phthalate)

Polyisobutylenesuccinic anhydride (1659 q) is dissolved in Solvent Naphtha Heavy fSAW, Saw (1220 g), end 3-dimethyiamlnoH -propylamine (DMAPA; 153 g) Is added. The reaction solution is stirred at 170⁴C for 8 h, in the course of which water of condensation formed Is distilled off continuously. This affords tiie P1BSA-DMAPA succinimide as a solution in Solvent Naphtha Heavy (TBN 0.557 mmoi/g),

A portion of this solution of the P1SSA-DMAPA succinimide (1S1 g) is added to dimethyl phthalate (19,4 g), and the resulting reaction solution is slimed at 120*0 for 11 h and then at 150^eC for 24 h. After cooling to room temperature, the product obtained is the ammonium carboxyiate as a solution in Solvent Naphtha Heavy, Ή NMR analysis confirms the quatemfzatlon.

Preparation example 2; Synthesis of an inventive quaternized succinimide {PIBSA/DMAPA/methyi salicylate)

Polyisobutylenesuccinic anhydride (PIBSA; 2198 g) is heated to 11CFC_S and 3dimethytemino-l-propylarnine (DMAPA; 182 g) is added within 40 min, In the course of which the reaction mixture heats up to 14EPC, The reaction mixture is heated to 170”C and held at this temperature for 3 h, in the course of which 28 g of dtetiilate are collected. This affords the PiBSA-DMAPA succinimide as a viscous oil (TBN 0,735 mmoVg),

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SO

A mixture of this PiBSA-DMAPA succinimide (284,5 g), methyl salicylate (85,5 g) (i.e. about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3,3,5-trlmethylheptenoic add (from BASF) (0,75 g) is heated to 140-150* and the reaction mixture is stirred at this temperature for 6 h. After cooling to room temperature, the product obtained is the ammonium salicylate as a viscous oil. Ή NMR analysis confirms the quatemizatfon, By adding Pitot 900 oil, Petrochem Carless Ltd,, the active ingredient content of the solution is adjusted to 50% by weight

Preparation example 3: Synthesis of an inventive quatemized succinimide (PlSSA/DMAPAtoimethyl oxalate)

Polyisobutylenesuccinic anhydride (PiSSA; 2198 g) Is heated to 110*C, and 3dlmethyiamino-1 -propylamine (DMAPA; 182 g) is added within 40 min, In the course of which the reaction mixture heats up to WC. The reaction mixture is heated to 170’C and held at this temperature for 3h, in the course of which 28 g of distillate are collected. This affords the PJBSA-DMAPA succinimide as a viscous oil (TBN 0735 mmol/g).

A mixture of this PIBSA-DMAPA succinimide (211 g), dimethyl oxalate (34,5 g) and

Iauric acid (4.9 g) is heated to 120*C and then stirred at this temperature for 4 h. Excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p - 5 mbar) at 120*C. The product obtained is the ammonium methyl oxalate as a viscous oii, ¹H NMR analysis confirms the quatemizatfon.

For comparison with the prior art, Examples 2 and 4 from WO 2008/135881 were worked up.

Preparation example 4: Synthesis of a blown quaternized succinimide (comparative example) (Example 2 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 oil, Pstrochem Cadess Ltd,, (51,3 g) is initially charged and heated to 110*0, DMAPA (31,4 g) is metered in within 50 minutes, in the course of which a slightly exothermic reaction is observed. Within 80 minutes, the reaction mixture is heated to 150’C and the mixture Is then kept at this temperature

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2019201700 13 Mar 2019 for 3 h, in the course of which, the water of reaction which forms is distilled off. After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution In Pitot 900 oil (TSN 0.52 mmol/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot 900 oil, Petrochem Carless Lid,, {354 g) is Initially charged and heated to 90’C. Dimethyl sulfate (26..3 g) is metered In, in the course of which the reaction temperature rises to 112’C, Subsequently, the reaction mixture is stirred at 100’C for 3-h. After cooling to room temperature, the quaternlzed PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil. ’H NMR confirmed the quaternization, The output was adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil.

Preparation example S: Synthesis of a known quatemized succtntmide (comparative example) (Example 4 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Carless Ltd., (51.3 g) is initially charged and heated to 110*0, DMAPA (31.4 g) is metered in within 50 minutes, in the course of which a slightly exothermic reaction is observed. Within 80 minutes, the reaction mixture Is heated to 150*0 and the mixture is then kept at this temperature for 3 h, in the course of which the water of reaction which forms Is dfotilied off. After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution In Pilot 900 oil (T8N 0.62 mrnol/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pitot 900 oil,

Petrochem Carless Ltd., ¢130 g), dimethyl carbonate (20 g) and methanol (17.4) are charged into an autoclave and inertteed with nitrogen, and a starting pressure of 1,3 bar is established.. Subsequently, the reaction mixture is stirred under autogenous pressure first at 90’C for 1 h, then at 140®C for 24 ft. After cooling to room temperature, the autoclave is decompressed and the contents are rinsed out completely with a little toluene as a solvent. All tow-boiling constituents are subsequently removed on a rotary evaporator under reduced pressure to obtain the quaternlzed PIBSA-DMAPA succinimide as a solution in Pilot 900 osi. ¹H NMR analysis confirmed the partial quatemlzation, The output is adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil.

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C. Use examples:

in the use examples which follow, the additives are used either as a pure substance 5 (as synthesized in the above preparation examples) or in the form of an additive package.

Ml: Additive according to preparation example 2 (Inventive, quatemized. with methyl salicylate)

M2: Additive according to preparation example 4 (comparative, quatemized with dimethyl sulfate)

M3: Additive according to preparation example 5 (comparative, quatemized with dimethyl carbonate)

Use example 1: determination of the additive action on the formation of deposits in diesel engine injection nozzles

a) XUD9 Teste

Fuel used: RP-06-03 (reference diesel, Haltermann Products, Hamburg)

The resuite are compiled in table 1:

Tabte 1: X.UDS teste j Name

I Dosage according to j Flow restriction J j preparation example |o,1 mm needle I (mg/kg) | stroke [%] J :3

#3 i#2

	M1, according to	30
	J»J*i .Sif kJ t $ t S U i to*' Al M2, according to	30
	preparation example 4
	M3, according to	30
	preparation example 5

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2019201700 13 Mar 2019 it was found that the inventive additive M1, with the same dosage, has an improved effect compared to the prior art (M2, M3),

b) DW10 test 5

To study the Influence of the inventive compound on the performance of direct-injection diesei engines, the power toss was determined based on the official test method CEC F-098-08 as described above. The power toss is a direct measure of formation of deposits in the Injectors. A conventional direct-injection diesei engine with a common10 rail system was used.

The fuel used was a commercial diesei fuel from Haltermann (RF-06-03). To synthetically induce the formation of deposits at the injectors, 1 ppm by weight of zinc in the form of a zinc didodecanoate solution was added thereto,

The table below shows the results of the determinations of the relative power loss at 4000 rpm after 12 hours of sustained operation without Interruption. The value Pe gives the power after 10 minutes and the value Ρ«χΐ the power at the end of the measurement:

The test results are shown in table 2.

Tapi© 2; Results of the DW10 test j Additive J

Isasevaiue,, I | M1, according to preparation J | example 2

,..L j M2, according to preparation | j example 4

M3, according to preparation j i example 5

.25 it was found that the inventive additive M1 has an improved effect compared to the base value and has an Improved affect at least compared to example M3.

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Use example 2: Determinate of the solubility properties

To determine the solubility properties, the following additive packages were produced end tested:

M 4 {inventive}

--------p™»™™---Substance Content [ppm] ]

Additive aoc, to preparation example 2	160.00
Dehazer, commercial	3.00
Antifoam, silicone-based, commercial	6.00
$
Solvent Naphtha Heavy	80.00
Tested 24S.00
M 5 (comparative, dimethyl sulfate)
Substance	Content [ppm]

«Additive acc, to preparation example 4	160.00
Dehazer, commercial	3.00
Antifoam, silicone-based, commercial	e.od
^Solvent Naphtha Heavy	420,00
Total	§89,00
M 6 (comparative, dimethyl carbonate)
Substance	Content [ppm]
Additive acc. to preparation example 5	160.00
Dehazer (commercial)	3.00
Antifoam, silicone-based, commercial	6.00
Solvent Naphtha Heavy	160,00
Total	319.00

The result of the solubility tests is compiled In the table below. The minimum amount of solvent (Solvent Naphtha Heavy) needed to obtain a homogeneous, clear diesel

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2019201700 13 Mar 2019 performance package at room temperature with otherwise identical amounts of active substance, Pilot 900, antifoam and dehazer is reported.

Table 3: Determination of the solvent requirement

Additive	Additive package	Minimum amount of solvent needed for a homogeneous package
PIBSA-DMAPA-imide-methyl salicylate	M4	32%
PIBSA-DMAPA-imide-dimethyl sulfate	M5	71%
PIBSA-DMAPA-imide-dimethyl carbonate	M6	47%

It was found that, surprisingly, the additive according to preparation example 2 has the best solubility properties, i.e. requires the least solvent.

Reference is made explicitly to the disclosure of the publications cited herein.

It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Also described herein are the following items 1 to 18:

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of 25 at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by a) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, especially capable of

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2019201700 13 Mar 2019 addition or condensation, with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and

b) subsequent reaction thereof with a quaternizing agent which converts the at least 5 one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid, especially dicarboxylic acid.

2. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid, especially dicarboxylic acid.

3. The fuel composition according to either of the preceding items, wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

4. The fuel composition according to any of the preceding claims, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of less than about 20% or less than about 15%.

5. The fuel composition according to any of the preceding items, wherein the quaternizing agent is a compound of the general formula 1

R1OC(O)R2 (1)

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2019201700 13 Mar 2019 in which

R1 is a lower alkyl radical and

R2 is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH2, NO2, C(O)OR3, and R1OC(O)-, in which R1 is as defined above and R3 is H or R1.

6. The fuel composition according to any of the preceding items, wherein the quaternizing agent is a compound of the general formula 2

R1OC(O)-A-C(O)OR1a (2) in which

R1 and R1a are each independently a lower alkyl radical and A is hydrocarbylene, such as especially alkylene or alkenylene.

7. The fuel composition according to any of the preceding items, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000, especially 800 to 3000 or 900 to 1500.

8. The fuel composition according to any of the preceding items, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates.

9. The fuel composition according to item 1, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a) hydroxyalkyl-substituted mono or polyamines having at least one quaternizable primary, secondary or tertiary amino group;

b) straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group;

c) piperazines.

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10. The fuel composition according to item 9, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxyilc acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a) hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines, b)straight-chain or branched aliphatic diamines having two primary amino groups; di or polyamines having at least one primary and at least one secondary amino group; di or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group.

11. The fuel composition according to any of the preceding items, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

12. A reaction product obtainable by a process as defined in any of the preceding items or quaternizable nitrogen compound obtained from the reaction product.

13. A process for preparing a quaternized nitrogen compound according to item 12, comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxyilc acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic monoor polycarboxyilc acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxyilc acid, especially dicarboxylic acid.

14. The use of a reaction product or of a quaternized nitrogen compound according to item 12 or of a compound prepared according to item 13 as a fuel additive.

15. The use according to item 14 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection

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2019201700 13 Mar 2019 systems, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems.

16. The use according to item 14 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

17. The use according to item 14 as a diesel fuel additive, especially as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, such as especially the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems.

18. An additive concentrate comprising, in combination with further diesel fuel or gasoline fuel additives, especially diesel fuel additives, at least one quaternized nitrogen compound as defined in item 12 or prepared according to item 13.

Claims (22)

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by al) reacting a hydrocarbyi-substituted polyoarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, with the polyoarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyi-substituted polyoarboxylic acid compound, and a2) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polyoarboxylic acid, or of an aliphatic polyoarboxylic acid; or

b) reacting a quaternizable hydrocarbyi-substituted polyoarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polyoarboxylic acid, or of an aliphatic polyoarboxylic acid wherein the hydrocarbyi-substituted polyoarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 70 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

2. The fuel composition according to claim 1, wherein the compound comprising at least one oxygen or nitrogen group is reactive with the polyoarboxylic acid by addition or condensation.

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3. The fuel composition according to claim 1 or 2, wherein said quaternizing agent is an alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxyiic acid, or of an aliphatic polycarboxylic acid.

4. The fuel composition according to any one of claims 1 to 3, wherein about 1.1 to 2.0 of quaternizing agent are used per equivalent of quatemizable tertiary nitrogen atom.

5. The fuel composition according to any one of claims 1 to 4, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quatemizable tertiary nitrogen atom.

6. The fuel composition according to any one of claims 1 to 5, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyisuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 80 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

7. The fuel composition according to any one of claims 1 to 6, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyisuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 85 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

8. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 1

RiOCtOM (1) in which

R! is a lower alkyl radical and

R₂ is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH₂, NO₂, C(O)OR₃, and R^CtO)-, in which R₂ is as defined above and R₃ is H or R₂.

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9. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 2

R!OC(O)-A-C(O)OR_la (2) in which

R^nd R_la are each independently a lower alkyl radical and A is hydrocarbylene.

10. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000.

11. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 800 to 3000.

12. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 900 to 1500.

13. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates.

14. The fuel composition according to any one of claims 1 to 13, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from

a. hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group;

b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group;

c. piperazines.

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15. The fuel composition according to claim 14, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quatemizable amino group is selected from

a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines,

b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group.

16. The fuel composition according to any one of the preceding claims, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

17. The use of a reaction product obtainable by a process as defined in any one of the preceding claims or of quaternized nitrogen compound obtained from the reaction product; or of a quaternized nitrogen compound prepared by a process comprising the reaction of a quatemizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quatemizable amino group with a quatemizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quatemizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid or of an aliphatic polycarboxylic acid; as a fuel additive, and wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, prepared by reacting polyisobutene having a proportion of vinylidene groups of greater than 70 mol% and having a polydispersity in the range from 1.1 to less than 1.9.

18. The use according to claim 17 as an additive for reducing the fuel consumption of direct-injection diesel engines, or diesel engines with common-rail injection systems, and/or for minimizing power loss in direct11167196_1 (GHMatters) P95787.AU.2

2019201700 13 Mar 2019 injection diesel engines, or in diesel engines with common-rail injection systems.

19. The use according to claim 17 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, or DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

20. The use according to claim 17 as a diesel fuel additive, as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, or in common-rail injection systems.

21. The use according to any one of claims 17 to 20, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

22. The use according to any one of claims 17 to 21, wherein said quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.